EP1957421B1 - Glass, glass-ceramic, articles and fabrication process - Google Patents
Glass, glass-ceramic, articles and fabrication process Download PDFInfo
- Publication number
- EP1957421B1 EP1957421B1 EP06841287.3A EP06841287A EP1957421B1 EP 1957421 B1 EP1957421 B1 EP 1957421B1 EP 06841287 A EP06841287 A EP 06841287A EP 1957421 B1 EP1957421 B1 EP 1957421B1
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- European Patent Office
- Prior art keywords
- glass
- sno
- ceramic material
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- 239000011521 glass Substances 0.000 title claims description 84
- 238000000034 method Methods 0.000 title claims description 25
- 230000008569 process Effects 0.000 title description 11
- 239000002241 glass-ceramic Substances 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 title description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 105
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 104
- 239000006112 glass ceramic composition Substances 0.000 claims description 98
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 70
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 30
- 239000006025 fining agent Substances 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 23
- 238000003279 ceramming Methods 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 229910052785 arsenic Inorganic materials 0.000 claims description 20
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 20
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 19
- 239000006064 precursor glass Substances 0.000 claims description 19
- 229910000500 β-quartz Inorganic materials 0.000 claims description 19
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 18
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 239000006104 solid solution Substances 0.000 claims description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000006018 Li-aluminosilicate Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000006060 molten glass Substances 0.000 claims description 5
- 238000010411 cooking Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 14
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- 229910052720 vanadium Inorganic materials 0.000 description 11
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 5
- 229960002594 arsenic trioxide Drugs 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000005398 lithium aluminium silicate glass-ceramic Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
Definitions
- the present invention relates to glass and glass-ceramic materials and process for making such materials.
- the present invention relates to glass-ceramic materials comprising ⁇ -quartz or(and) ⁇ -spodumene solid solution(s) as the predominant crystalline phase(s), articles comprising such materials, and process of making such glass-ceramic materials and articles.
- the present invention is useful, for example, in making glass-ceramic material for use in cooktops, furnace windows and the like.
- Glass-ceramic materials comprise crystalline phases and glassy phases. Due to the unique structures, they have exceptional physical properties, such as strength and coefficient of thermal expansion that enable them to be used in a wide range of products.
- a particularly interesting application of ⁇ -quartz and/or ⁇ -spodumene glass-ceramic material is in cooktop plates, fireplace windows and the like. A series of glass-ceramic cooktop plates and fireplace windows have been commercialized successfully.
- the fabrication process of glass-ceramic material typically includes three steps: (i) melting of the precursor glass; (ii) forming the precursor glass into desired shapes; and (iii) heat-treating the shaped glass object to such that crystalline phases are formed in the glass article.
- the last step typically comprises two steps: (iii-a) treating the glass article at a relatively lower temperature where crystalline nuclei are allowed to form, which is typically termed the step of nucleating; and (iii-b) treating the glass article with nuclei at a higher temperature where the crystalline phase is allowed to grow to a desired extent.
- a fining agent is employed in making the precursor glass.
- Such fining agent releases gas at elevated temperature where the glass is melted and fined. The released gas facilitates the escaping of the gas bubbles which would otherwise be trapped inside the glass.
- As 2 O 3 and/or Sb 2 O 3 were used as effective fining agents. Due to increasing environmental concerns, As 2 O 3 and Sb 2 O 3 are to be phased out from such products in the near future. Therefore, there is the need of developing an alternative fining system that can effectively fine the glass during the glass melting step without significantly negatively impacting the forming step and the desired properties of the intended glass-ceramic articles and the fabrication process.
- Document US 2005/0252503 discloses lithium-alumino-silicate glass-ceramics, the composition of which contains at least one fining agent, from the group consisting of As 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , sulfate and/or chloride compounds, in a total amount of up to 0.8 wt. %. Its example 13 more specifically discloses a glass-ceramic free from arsenic and antimony and the base composition of which is doped with the coloring ingredients identified: SnO 2 (0.25 wt. %), V 2 O 5 (0.003 wt. %) and CeO 2 (0.1 wt. %).
- the present invention satisfies this need.
- a glass-ceramic material containing a solid solution of ⁇ -quartz or(and) ⁇ -spodumene, as main crystalline phase(s), and essentially free of arsenic and antimony, characterized in that its composition, expressed in percentages by weight of oxides, is as specified in following paragraph [0009] (it actually comprises 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO 2 ; and 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO 2 and/or MnO 2 ).
- the glass-ceramic material of the present invention comprises both SnO 2 and CeO 2 .
- the glass-ceramic material of the present invention comprises both SnO 2 and MnO 2 .
- the glass-ceramic material of the present invention has a composition, expressed in terms of weight percentage on an oxide basis, consisting essentially of: SiO 2 50-75; Al 2 O 3 17-27; Li 2 O 2-6; MgO 0-5; ZnO 0-5; TiO 2 0-5; ZrO 2 0-5; BaO 0-3; SrO 0-3; CaO 0-3; Na 2 O 0-3; K 2 O 0-3; P 2 O 5 0-8; B 2 O 3 0-3; SnO 2 0.15-0.3; CeO 2 and/or MnO 2 0.7-1.5.
- the glass-ceramic material of the present invention has a composition, expressed in terms of weight percentage on an oxide basis, consisting essentially of: SiO 2 65-70; Al 2 O 3 18-22; Li 2 O 2.5-4; MgO 0,5-2; ZnO 1-3; TiO 2 1.5-3.5; ZrO 2 0-2.5; BaO 0-2; SrO 0-2; CaO 0-2; Na 2 O 0-1; K 2 O 0-1.5; P 2 O 5 0-3; SnO 2 0.15-0.25; CeO 2 and/or MnO 2 0.8-1.5.
- the glass-ceramic material of the present invention has a composition, expressed in terms of weight percentage on an oxide basis, consisting essentially of: SiO 2 65-70; Al 2 O 3 18-19.8; Li 2 O 2.5-3.8; MgO 0.55-1.5; ZnO 1.2-2.8; TiO 2 1.8-3.2; BaO 0-1.4; SrO 0-1.4, with BaO+SrO 0.4-1.4, with MgO+BaO+SrO 1.1-2.3; ZrO 2 1.0-2.5; Na 2 O 0- ⁇ 1.0; K 2 O 0- ⁇ 1.0, with Na 2 O + K 2 O, 0- ⁇ 1.0, with (2.8Li 2 O+1.2ZnO)/5.2MgO >1.8; SnO 2 0.15-0.3 advantageously 0.15 to 0.25%; CeO 2 and/or MnO 2 0.7-1.5 advantageously 0.8 to 1.5%.
- the composition of which further comprises an effective amount of at least one colorant, advantageously selected from CoO, Cr 2 O 3 , Fe 2 O 3 , NiO, CuO and V 2 O 5 .
- a second aspect of the present invention involves a article made of the glass-ceramic material of the present invention described summarily supra and in detail infra , which is a cook-top, a cooking utensil, a microwave oven plate, a fireplace window, a fire-door, a fire-window, a pyrolysis- or catalysis-oven window.
- a third aspect of the present invention involves the precursor glass of the glass-ceramic material described summarily supra and in detail infra .
- a fourth aspect of the present invention is a process for making the glass-ceramic material of the present invention described summarily supra and in detail infra , which comprises heat-treating a lithium alumino-silicate glass, which is a precursor of such a glass-ceramic material, under conditions which ensure its ceramming, said glass containing, with the exception of inevitable traces, neither arsenic, nor antimony, characterized in that the composition of said glass corresponds to that of a glass-ceramic material of the invention (expressed in percentages by weight of oxides, it comprises: 0.15-0.3%, advantageously 0.15 to 0.25%, of SnO 2 ; and 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO 2 and/or MnO 2 ).
- Certain embodiments of the process of the present invention are further characterized in that SnO2 and CeO2 and/or MnO2 are effectively used, in the indicated amounts, for fining the said precursor glass.
- composition of said glass or said filler comprises an effective amount of at least one metallic oxide-type colorant, the metal of which is able to exist under different valences, advantageously consisting in V 2 O 5 ; and in that SnO 2 and CeO 2 and/or MnO 2 are effectively used, in the indicated amounts, for fining the said precursor glass and stabilizing the color of the glass-ceramic material during aging.
- a fifth aspect of the present invention relates to the use of SnO 2 in combination with CeO 2 and/or MnO 2 , in the below amounts, expressed in percentages by weight of oxides of the composition of said glass, for the fining of a glass which is the precursor of a glass-ceramic material containing a solid solution of ⁇ -quartz or(and) ⁇ -spodumene as main crystalline phase(s) and, with the exception of inevitable traces, neither arsenic, nor antimony:
- a sixth aspect of the present invention relates to the use of SnO 2 in combination with CeO 2 and/or MnO 2 , in the below amounts expressed in percentages by weight of oxides of the composition of said glass:
- the present invention has at its object:
- the present invention also has at its object the use of a specific combination of compounds in the fining of a precursor glass, and even in the said fining and in the stabilization of the color in the ageing of the colored glass-ceramic material (by the action within of at least one metallic-oxide dye whose metal element is likely to exist with several valences, such as V 2 O 5 ) obtained from such a glass.
- Said present invention rests on the action, within compositions of the aforesaid glass-ceramic materials and glasses, of a specific combination of compounds to provide, in particular, the glass fining function.
- Glass-ceramic materials which contain a solid solution of ⁇ -quartz or of ⁇ -spodumene(solid solutions of ⁇ -quartz and ⁇ -spodumene) as main crystalline phase(s) are materials known per se, obtained by heat treatment of glasses or mineral fillers. These materials are used in various contexts, notably as a substrate for cooktops and fire windows.
- Transparent, opalescent, and even opaque glass ceramics are known in a variety of colors.
- At least one fining agent is used.
- Arsenic oxide (As 2 O 3 ) has generally been used in the methods hitherto, typically at greater than 0.1% and less than 1% by weight.
- Antimony oxide (Sb 2 O 3 ) has also been used at higher ratios.
- arsenic oxide can act to confer a color, generally dark, to the glass-ceramic materials which contain it. It acts, to this end, on the vanadium (a metallic element likely to exist under several valences) present.
- the vanadium present - generally added at approximately 0.2% by weight - is mainly in an oxidized state (V 5+ ) and the aforesaid glass presents only weak coloring.
- arsenic reduces vanadium (in V 4+ and/or V 3+ form); this leads to strong absorption in the visible and near infrared ranges and in the end gives the glass-ceramic material a dark color.
- Patent applications JP 11 100 229 and 11 100 230 describe such a use of tin oxide (SnO 2 ), alone or in combination with chlorine (Cl), at a level of: SnO 2 : 0.1-2% by weight; and Cl: 0-1% by weight.
- SnO 2 tin oxide
- Cl chlorine
- the inventor confronted with this technical problem of providing fining agents to substitute for As 2 O 3 and/or Sb 2 O 3 , studied the performance of SnO 2 and demonstrated that this compound is not, alone, completely satisfactory.
- SnO 2 + CeO 2 and/or MnO 2 combinations and for having observed, surprisingly, that such specific combinations are effective as a fining agent for precursor glass and as a stabilizer at ageing for the color of the colored glass-ceramic material obtained from such a glass.
- SnO 2 acts at low levels and thus the problems mentioned above are minimized or even avoided.
- SnO 2 , CeO 2 , and MnO 2 When added to a mixture of vitrifiable raw materials, SnO 2 , CeO 2 , and MnO 2 each tend to release oxygen when the temperature of the bath of glass increases, which a priori supports the fining phenomenon.
- the quantity of oxygen released and the temperature interval over which it is released depend on the redox equilibria established between the various multivalent elements present in the aforesaid bath of glass.
- the first object of the present invention relates to glass-ceramic materials containing a solid solution of ⁇ -quartz or of ⁇ -spodumene(solid solutions of ⁇ -quartz and ⁇ -spodumene) as main crystalline phase(s), and containing with the exception of inevitable traces, neither arsenic (As) nor antimony (Sb), whose composition, expressed in percentages by weight of oxides with respect to total weight, comprises:
- the aforesaid glass-ceramic materials characteristically contain tin oxide in a non-excessive quantity ( ⁇ 0.3% by weight), in reference to the problems mentioned above. They also contain cerium oxide and/or manganese oxide in a non-excessive quantity ( ⁇ 1.5% by weight), mainly in reference to problems of coloring. They contain the aforesaid tin, cerium, and/or manganese oxides in the minimal quantities indicated (SnO 2 ⁇ 0.15%; CeO 2 and/or MnO 2 ⁇ 0.7%), in reference to the efficiency sought, mainly at the level of fining.
- the aforesaid glass-ceramic materials contain these compounds in an original and characteristic way, in the quantities indicated, in reference to the technical problems described above, mainly that of the fining of glass precursors of the aforesaid glass-ceramic materials.
- SnO 2 and CeO 2 are advantageously found in the quantities indicated above.
- As 2 O 3 and/or Sb 2 O 3 are not present, supposing that they are present, in effective quantities, in reference to the fining of precursor glasses of the aforesaid glass-ceramic materials. If As and/or Sb are present, they are as trace elements, in quantities generally lower than 200 ppm. The presence of such traces can not be excluded. The aforesaid traces come, for example, from impurities in the raw materials used. The specific details above are given in reference to the circumlocution "containing, with the exception of inevitable traces, neither arsenic nor antimony" used in the present description and the appended claims, to qualify glass-ceramic materials and their precursor glasses.
- the glass-ceramic materials of the invention may not, however, be excluded that the glass-ceramic materials of the invention contain others active compounds as a fining agent. It is only according to an advantageous embodiment that they do not contain such compounds.
- the glass-ceramic materials of the invention do not contain fluorine.
- glass-ceramic materials of the first object of the invention whose composition, expressed in percentages of oxide weight, essentially consists of: SiO 2 50-75 advantageously 65-70 Al 2 O 3 17-27 advantageously 18-22 Li 2 O 2-6 advantageously 2.5-4 MgO 0-5 advantageously 0.5-2 ZnO 0-5 advantageously 1-3 TiO 2 0-5 advantageously 1.5-3.5 ZrO 2 0-5 advantageously 0-2.5 BaO 0-3 advantageously 0-2 SrO 0-3 advantageously 0-2 CaO 0-3 advantageously 0-2 Na 2 O 0-3 advantageously 0-1 K 2 O 0-3 advantageously 0-1.5 P 2 O 5 0-8 advantageously 0-3 B 2 O 3 0-3 SnO 2 0.15-0.3 advantageously 0.15-0.25 CeO 2 and/or MnO 2 0.7-1.5 advantageously 0.8-1.5
- the glass-ceramic materials of the invention advantageously present the weight composition indicated above in the rightmost column.
- compositions in question "essentially consist of” the given list of oxides. This means that within the aforesaid compositions the sum of the listed oxides represents at least 95%, generally at least 98% by weight. Indeed, other elements such as lanthanum oxide, yttrium oxide, and dyes (see further), in small quantities, may be found within the aforesaid compositions.
- glass-ceramic materials with interesting properties, in particular rapid ceramming.
- Such glass-ceramic materials are advantageously related to the present invention.
- glass-ceramic materials also part of the first object of the invention whose composition expressed in percentages of oxide weight essentially consists of: SiO 2 65-70 Al 2 O 3 18-19.8 Li 2 O 2.5-3.8 MgO 0.55-1.5 ZnO 1.2-2.8 TiO 2 1.8-3.2 BaO 0-1.4 SrO 0-1.4 with BaO+ SrO 0.4-1.4 with MgO+ BaO+ SrO 1.1-2.3 ZrO 2 1.0-2.5 Na 2 O 0- ⁇ 1.0 K 2 O 0- ⁇ 1.0 with Na 2 O+ K 2 O 0- ⁇ 1.0 With (2.8 Li 2 O+1.2 ZnO) /5.2 MgO >1.8 SnO 2 0.15-0.3 CeO 2 and/or MnO 2 0.7-1.5
- the glass-ceramic materials of the invention are likely to contain dyes. Their composition is thus likely to contain an effective quantity (in reference to the coloring effect sought) of at least one dye.
- Said dye or dyes are advantageously selected from among CoO, Cr 2 O 3 , Fe 2 O 3 , NiO, CuO, and V 2 O 5 (thus taken separately or in combination).
- V 2 O 5 a metallic oxide dye whose metal element, vanadium, is likely to exist with several valences
- glass-ceramic materials of the invention contain advantageously 0.03 to 0.15% vanadium oxide.
- the second object of the present invention relates to glass-ceramic articles as described above, said glass-ceramic material containing jointly in its composition SnO 2 and CeO 2 and/or MnO 2 in the quantities specified above.
- the aforesaid articles can in particular consist of cook-tops, cooking utensils, microwave oven plates, fireplace windows, fire doors, fire windows, and pyrolysis- and catalysis-oven windows. Such a list is not exhaustive.
- the third object of the present invention relates to lithium alumino-silicate glasses, which are precursors of glass-ceramic materials of the invention, such as described above.
- the lithium alumino-silicate glasses which jointly contain SnO 2 and CeO 2 and/or MnO 2 , in the quantities specified above, and which are precursors of the glass-ceramic materials of the invention, are in fact novel and therefore constitute the third object of the invention.
- Said novel glasses advantageously present a composition that corresponds to those specified above for the glass-ceramic materials of the invention.
- the aforesaid novel glasses present a composition which contains, except for inevitable traces, neither arsenic nor antimony.
- the aforesaid novel glasses only contain as a fining agent the combination "SnO 2 + CeO 2 and/or MnO 2 " within the meaning of the invention.
- the fourth object of the present invention relates to a method of preparing a glass-ceramic material of the invention, such as described above.
- said method comprises the heat treatment of a lithium alumino-silicate glass, which is a precursor of such a glass-ceramic material, under conditions which ensure its ceramming, the aforesaid glass containing, with the exception of inevitable traces, neither arsenic nor antimony.
- a ceramming treatment is known per se.
- the glass-ceramic materials produced advantageously present a composition which corresponds to one of the compositions specified above for the glass-ceramic materials of the invention.
- the fifth object of the present invention relates to a method of preparing an article made from a glass-ceramic material of the invention.
- the aforesaid method classically comprises three successive steps as follows:
- the aforesaid glass or the aforesaid filler in question presents a composition which contains jointly tin oxide and cerium oxide and/or manganese oxide in the quantities below, expressed in percentages by weight of oxides with respect to total weight:
- the glass-ceramic material component of the article produced advantageously presents a composition which corresponds to one of the compositions specified above for glass-ceramic materials of the invention.
- SnO 2 and CeO 2 and/or MnO 2 act efficiently, in the quantities indicated, for the fining of precursor glass.
- the composition of glass or filler includes an effective quantity of at least one metallic oxide dye whose metallic element is likely to exist with several valences (advantageously V 2 O 5 ) and SnO 2 and CeO 2 and/or MnO 2 act efficiently in the quantities indicated for the simultaneous fining of precursor glass and the stabilization of the color of the glass-ceramic materials during ageing.
- SnO 2 and CeO 2 and/or MnO 2 act advantageously in the preparation of glass-ceramic material articles colored with vanadium, in the preparation of dark glass-ceramic plates, in particular, intended for cooking.
- the reduction in the transmission of glass-ceramic materials during the ageing process is related to the continuation of the reduction of vanadium.
- the inventor thus observed, within the scope of this invention, that the presence of manganese and/or cerium oxide limits the reduction of vanadium and consequently makes it possible to better control glass-ceramic coloring properties.
- examples E, F, H and I illustrate the aforesaid invention while examples A, B, C, D and G are comparative examples.
- Glasses were prepared in the usual way from oxides and/or easily decomposable compounds such as nitrates and carbonates. The raw materials are mixed to obtain a homogeneous mixture.
- the glasses were then rolled to a thickness of 6 mm and then heated at 650 °C for 1 h.
- the number of bubbles was automatically counted by a camera coupled to an image analyzer.
- the melting cycle is short in order to generate sufficient bubbles for the purpose of differentiating the fining performances of the various products tested (As 2 O 3 , SnO 2 , CeO 2 , SnO 2 + CeO 2 , SnO 2 + MnO 2 ). It can be estimated that the glass obtained from this test with fewer than 400 bubbles/cm 3 can be produced on an industrial scale with sufficient quality.
- fining according to the invention does not significantly modify the properties (thermal dilation, color and transmission) of prepared glass-ceramic materials and that, on the contrary, a positive effect on ageing is observed.
- the raw materials were brought to 1,500 °C then melting was performed at 1,650 °C for 6 h.
- the glass was rolled to a thickness of 6 mm and reheated at 650 °C for 1 h.
- Ageing is performed for 100 h at 700 °C in a static oven. After the aforesaid ageing, the thermal expansion coefficient, integrated transmission Y, and transmission at 1,050 nm are again measured.
- compositions of glasses and glass-ceramic materials as well as the properties of the aforesaid glass-ceramic materials are given in Table 2 below.
- sample in example G contains only tin oxide (SnO 2 ), while those in examples H and I (invention) contain SnO 2 + CeO 2 and SnO 2 + MnO 2 , respectively, in adequate quantities as a fining agent.
- transmission as a function of wavelength was measured on samples 0.5 mm in thickness after ceramming (G', H') and after ceramming and ageing (G", H").
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Description
- The present invention relates to glass and glass-ceramic materials and process for making such materials. In particular, the present invention relates to glass-ceramic materials comprising β-quartz or(and) β-spodumene solid solution(s) as the predominant crystalline phase(s), articles comprising such materials, and process of making such glass-ceramic materials and articles. The present invention is useful, for example, in making glass-ceramic material for use in cooktops, furnace windows and the like.
- Glass-ceramic materials comprise crystalline phases and glassy phases. Due to the unique structures, they have exceptional physical properties, such as strength and coefficient of thermal expansion that enable them to be used in a wide range of products. A particularly interesting application of β-quartz and/or β-spodumene glass-ceramic material is in cooktop plates, fireplace windows and the like. A series of glass-ceramic cooktop plates and fireplace windows have been commercialized successfully.
- The fabrication process of glass-ceramic material typically includes three steps: (i) melting of the precursor glass; (ii) forming the precursor glass into desired shapes; and (iii) heat-treating the shaped glass object to such that crystalline phases are formed in the glass article. The last step typically comprises two steps: (iii-a) treating the glass article at a relatively lower temperature where crystalline nuclei are allowed to form, which is typically termed the step of nucleating; and (iii-b) treating the glass article with nuclei at a higher temperature where the crystalline phase is allowed to grow to a desired extent.
- As is typical in glass melting, in step (i), a fining agent is employed in making the precursor glass. Such fining agent releases gas at elevated temperature where the glass is melted and fined. The released gas facilitates the escaping of the gas bubbles which would otherwise be trapped inside the glass. Historically, As2O3 and/or Sb2O3 were used as effective fining agents. Due to increasing environmental concerns, As2O3 and Sb2O3 are to be phased out from such products in the near future. Therefore, there is the need of developing an alternative fining system that can effectively fine the glass during the glass melting step without significantly negatively impacting the forming step and the desired properties of the intended glass-ceramic articles and the fabrication process. Document
US 2005/0252503 discloses lithium-alumino-silicate glass-ceramics, the composition of which contains at least one fining agent, from the group consisting of As2O3, Sb2O3, SnO2, CeO2, sulfate and/or chloride compounds, in a total amount of up to 0.8 wt. %. Its example 13 more specifically discloses a glass-ceramic free from arsenic and antimony and the base composition of which is doped with the coloring ingredients identified: SnO2 (0.25 wt. %), V2O5 (0.003 wt. %) and CeO2 (0.1 wt. %). - The present invention satisfies this need.
- According to a first aspect of the present invention, provided is a glass-ceramic material containing a solid solution of β-quartz or(and) β-spodumene, as main crystalline phase(s), and essentially free of arsenic and antimony, characterized in that its composition, expressed in percentages by weight of oxides, is as specified in following paragraph [0009] (it actually comprises 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO2; and 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2).
- According to certain embodiment of the glass-ceramic material of the present invention, it comprises both SnO2 and CeO2.
- According to certain other embodiments of the glass-ceramic material of the present invention, it comprise both SnO2 and MnO2.
- The glass-ceramic material of the present invention has a composition, expressed in terms of weight percentage on an oxide basis, consisting essentially of: SiO2 50-75; Al2O3 17-27; Li2O 2-6; MgO 0-5; ZnO 0-5; TiO2 0-5; ZrO2 0-5; BaO 0-3; SrO 0-3; CaO 0-3; Na2O 0-3; K2O 0-3; P2O5 0-8; B2O3 0-3; SnO2 0.15-0.3; CeO2 and/or MnO2 0.7-1.5.
- According to certain embodiments of the glass-ceramic material of the present invention, it has a composition, expressed in terms of weight percentage on an oxide basis, consisting essentially of: SiO2 65-70; Al2O3 18-22; Li2O 2.5-4;
MgO 0,5-2; ZnO 1-3; TiO21.5-3.5; ZrO2 0-2.5; BaO 0-2; SrO 0-2; CaO 0-2; Na2O 0-1; K2O 0-1.5; P2O5 0-3; SnO2 0.15-0.25; CeO2 and/or MnO2 0.8-1.5. - According to certain embodiments of the glass-ceramic material of the present invention, it has a composition, expressed in terms of weight percentage on an oxide basis, consisting essentially of: SiO2 65-70; Al2O3 18-19.8; Li2O 2.5-3.8; MgO 0.55-1.5; ZnO 1.2-2.8; TiO2 1.8-3.2; BaO 0-1.4; SrO 0-1.4, with BaO+SrO 0.4-1.4, with MgO+BaO+SrO 1.1-2.3; ZrO2 1.0-2.5; Na2O 0-<1.0; K2O 0-<1.0, with Na2O + K2O, 0-<1.0, with (2.8Li2O+1.2ZnO)/5.2MgO >1.8; SnO2 0.15-0.3 advantageously 0.15 to 0.25%; CeO2 and/or MnO2 0.7-1.5 advantageously 0.8 to 1.5%.
- According to certain embodiments of the glass-ceramic material of the present invention, the composition of which further comprises an effective amount of at least one colorant, advantageously selected from CoO, Cr2O3, Fe2O3, NiO, CuO and V2O5.
- A second aspect of the present invention involves a article made of the glass-ceramic material of the present invention described summarily supra and in detail infra, which is a cook-top, a cooking utensil, a microwave oven plate, a fireplace window, a fire-door, a fire-window, a pyrolysis- or catalysis-oven window.
- A third aspect of the present invention involves the precursor glass of the glass-ceramic material described summarily supra and in detail infra.
- A fourth aspect of the present invention is a process for making the glass-ceramic material of the present invention described summarily supra and in detail infra, which comprises heat-treating a lithium alumino-silicate glass, which is a precursor of such a glass-ceramic material, under conditions which ensure its ceramming, said glass containing, with the exception of inevitable traces, neither arsenic, nor antimony, characterized in that the composition of said glass corresponds to that of a glass-ceramic material of the invention (expressed in percentages by weight of oxides, it comprises: 0.15-0.3%, advantageously 0.15 to 0.25%, of SnO2; and 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2).
- According to certain embodiments of the process of the present invention, it successively comprises the following steps:
- melting a lithium alumino-silicate glass or an inorganic filler, which is a precursor of such a glass, said glass or said filler containing, with the exception of inevitable traces, neither arsenic, nor antimony and containing an effective and non-excess amount of at least one fining agent; followed by fining the molten glass obtained;
- cooling the molten fined glass obtained and, simultaneously, shaping it into the shape desired for the article sought after;
- ceramming said shaped glass,
- Certain embodiments of the process of the present invention are further characterized in that SnO2 and CeO2 and/or MnO2 are effectively used, in the indicated amounts, for fining the said precursor glass.
- Certain embodiments of the process of the present invention are further characterized in that the composition of said glass or said filler comprises an effective amount of at least one metallic oxide-type colorant, the metal of which is able to exist under different valences, advantageously consisting in V2O5; and in that SnO2 and CeO2 and/or MnO2 are effectively used, in the indicated amounts, for fining the said precursor glass and stabilizing the color of the glass-ceramic material during aging.
- A fifth aspect of the present invention relates to the use of SnO2 in combination with CeO2 and/or MnO2, in the below amounts, expressed in percentages by weight of oxides of the composition of said glass, for the fining of a glass which is the precursor of a glass-ceramic material containing a solid solution of β-quartz or(and) β-spodumene as main crystalline phase(s) and, with the exception of inevitable traces, neither arsenic, nor antimony:
- 0.15 to 0.3%, advantageously 0.15 to 0.25% of SnO2; and
- 0.7 to 1.5%, advantageously 0.8 to 1.5% of CeO2 and/or MnO2.
- A sixth aspect of the present invention relates to the use of SnO2 in combination with CeO2 and/or MnO2, in the below amounts expressed in percentages by weight of oxides of the composition of said glass:
- 0.15 to 0.3%, advantageously 0.15 to 0.25% of SnO2; and
- 0.7 to 1.5%, advantageously 0.8 to 1.5% of CeO2 and/or MnO2,
- (A) the fining of a glass which is the precursor glass of a glass-ceramic material containing (i) a solid solution of β-quartz or(and) of β-spodumene as main crystalline phase(s); (ii) an effective amount of at least one metallic oxide-type colorant, the metal of which is able to exist under different valences; and (iii) with the exception of inevitable traces, neither arsenic, nor antimony, and containing advantageously consisting in V2O5; and
- (B) stabilizing the color of the glass-ceramic material obtained from said glass during ageing.
- The sole drawing,
Figure1 , is a diagram showing the light transmission curve of a series of glass-ceramic materials. - The present invention has at its object:
- novel glass-ceramic materials containing a solid solution of β-quartz or of β-spodumene(solid solutions of β-quartz and β-spodumene), as main crystalline phase(s);
- articles made from said novel glass-ceramic materials;
- lithium alumino-silicate glasses, precursors of such novel glass-ceramic materials;
- methods of preparing the aforesaid novel glass-ceramic materials and the aforesaid articles made from said novel glass-ceramic materials.
- The present invention also has at its object the use of a specific combination of compounds in the fining of a precursor glass, and even in the said fining and in the stabilization of the color in the ageing of the colored glass-ceramic material (by the action within of at least one metallic-oxide dye whose metal element is likely to exist with several valences, such as V2O5) obtained from such a glass.
- Said present invention rests on the action, within compositions of the aforesaid glass-ceramic materials and glasses, of a specific combination of compounds to provide, in particular, the glass fining function.
- Glass-ceramic materials which contain a solid solution of β-quartz or of β-spodumene(solid solutions of β-quartz and β-spodumene) as main crystalline phase(s) are materials known per se, obtained by heat treatment of glasses or mineral fillers. These materials are used in various contexts, notably as a substrate for cooktops and fire windows.
- Transparent, opalescent, and even opaque glass ceramics are known in a variety of colors.
- The manufacture of β-quartz and/or β-spodumene glass-ceramic articles classically includes three principal, successive steps:
- a first step of melting an inorganic glass or a filler, a precursor of such a glass, generally performed at a temperature between 1,550 and 1,650 °C,
- a second step of cooling and shaping the molten glass obtained, and
- a third step of crystallizing or ceramming the cooled, shaped glass by a suitable heat treatment.
- Following the initial melting step, it is important to eliminate gaseous inclusions from the mass of molten glass as efficiently as possible. To this end at least one fining agent is used.
- Arsenic oxide (As2O3) has generally been used in the methods hitherto, typically at greater than 0.1% and less than 1% by weight. Antimony oxide (Sb2O3) has also been used at higher ratios.
- Given the toxicity of these products and the increasingly drastic regulations in effect (with respect to environmental safety and protection), avoidance of the use of these products is sought; other less-toxic, even non-toxic compounds to be used as fining agents are being researched.
- For obvious reasons of economy, however, modification of current industrial methods is not desired. In particular, operation at higher temperature, with the implied increase in energy requirements and worsening of problems related to corrosion, is not desired.
- Thus are sought compounds other than arsenic oxide and antimony oxide that, using the same methods, are effective as fining agents (substitutes for said oxides) for the glass which is to be cerammed.
- Over and above its role as a fining agent, arsenic oxide can act to confer a color, generally dark, to the glass-ceramic materials which contain it. It acts, to this end, on the vanadium (a metallic element likely to exist under several valences) present. In precursor glass, the vanadium present - generally added at approximately 0.2% by weight - is mainly in an oxidized state (V5+) and the aforesaid glass presents only weak coloring. During ceramming, arsenic reduces vanadium (in V4+ and/or V3+ form); this leads to strong absorption in the visible and near infrared ranges and in the end gives the glass-ceramic material a dark color. However, during ceramming, the reaction between arsenic and vanadium is never complete; the reaction tends to continue when the glass-ceramic material is later heated. Thus, a reduction in visible and infrared transmission is observed when the glass-ceramic material undergoes a process known as ageing for 100 h at 700 °C. In view of the remarks above, it is sincerely hoped that the substitute compounds for arsenic oxide to be used as a glass fining agent do not interfere with obtaining, after ceramming, of the dark color, when it is desired, and it would be additionally advantageous if they ensure better stability of the aforesaid dark color from ageing.
- Numerous documents of the prior art -
JP 11 100 229 JP 11 100 230 DE 19 939787.2 ,WO 02/16279 EP 0 156 479US 5 446 008 ,US 6 673 729 , andEP 1 398 303 - provide for the action of SnO2 and CeO2 separately (SnO2 or CeO2) or in combination (SnO2 and CeO2), as a fining agent for precursor glasses of glass-ceramic materials. The aforesaid documents do not, however, include a description of specific SnO2 and CeO2 combinations. - The use of SnO2 (independently of CeO2) was, on the other hand, expressly illustrated as a fining agent.
- Patent applications
JP 11 100 229 11 100 230 - Applications
DE 19 939 787.2 andWO 02/16279 - The inventor, confronted with this technical problem of providing fining agents to substitute for As2O3 and/or Sb2O3, studied the performance of SnO2 and demonstrated that this compound is not, alone, completely satisfactory.
- The efficiency of SnO2, as a fining agent for precursor glasses of glass-ceramic materials, increases with the quantity of use of the aforesaid SnO2. It is thus possible to obtain good results with respect to the fining of the aforesaid glasses, good results that are nearly comparable with those obtained to date with As2O3 in particular, by using adequate quantities of SnO2. However, the action of these adequate, effective quantities from the point of view of fining is detrimental:
- first, because of the low solubility of SnO2 in glass. Problems of devitrification and difficulties of implementation of the melting are very quickly observed; and
- second, because of the reduction power of SnO2. SnO2 is likely to reduce transition metal oxides present in glass, in particular vanadium oxide, and thus to strongly influence the color of the ceramic concerned. In its presence, at quantities effective for fining precursor glass, the color of the final glass-ceramic material is difficult to control.
- It is thus clear that it is not satisfactory to propose to use SnO2 as an effective fining agent instead of conventional fining agents (As2O3 and/or Sb2O3).
-
- Lastly, some documents of the prior art mention the use of SnO2, CeO2, and/or MnO2, as dyes.
US patent 4,461,830 thus describes glass-ceramic materials containing As2O3 as a fining agent whose coloring filler is likely to contain CeO2 (from 0 to 3% by weight) and SnO2 (from 0 to 1.5% by weight). No example illustrates the joint action of CeO2 and SnO2. - The inventor deserves credit for having demonstrated, in such a context, the interest of specific "SnO2 + CeO2 and/or MnO2" combinations and for having observed, surprisingly, that such specific combinations are effective as a fining agent for precursor glass and as a stabilizer at ageing for the color of the colored glass-ceramic material obtained from such a glass. Within the aforesaid combinations, SnO2 acts at low levels and thus the problems mentioned above are minimized or even avoided.
- When added to a mixture of vitrifiable raw materials, SnO2, CeO2, and MnO2 each tend to release oxygen when the temperature of the bath of glass increases, which a priori supports the fining phenomenon. The quantity of oxygen released and the temperature interval over which it is released depend on the redox equilibria established between the various multivalent elements present in the aforesaid bath of glass.
- Surprisingly, it was observed that specific "SnO2 + CeO2 and/or MnO2" combinations of the invention are particularly effective.
- Thus, the first object of the present invention relates to glass-ceramic materials containing a solid solution of β-quartz or of β-spodumene(solid solutions of β-quartz and β-spodumene) as main crystalline phase(s), and containing with the exception of inevitable traces, neither arsenic (As) nor antimony (Sb), whose composition, expressed in percentages by weight of oxides with respect to total weight, comprises:
- 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO2; and
- 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2.
- The aforesaid glass-ceramic materials characteristically contain tin oxide in a non-excessive quantity (≤ 0.3% by weight), in reference to the problems mentioned above. They also contain cerium oxide and/or manganese oxide in a non-excessive quantity (≤ 1.5% by weight), mainly in reference to problems of coloring. They contain the aforesaid tin, cerium, and/or manganese oxides in the minimal quantities indicated (SnO2 ≥ 0.15%; CeO2 and/or MnO2 ≥ 0.7%), in reference to the efficiency sought, mainly at the level of fining.
- The aforesaid glass-ceramic materials contain these compounds in an original and characteristic way, in the quantities indicated, in reference to the technical problems described above, mainly that of the fining of glass precursors of the aforesaid glass-ceramic materials.
- Within the glass-ceramic materials of the invention, SnO2 and CeO2, or SnO2 and MnO2 are advantageously found in the quantities indicated above.
- Recommended "SnO2 + CeO2 and/or MnO2" combinations are effective and undoubtedly make it possible to dispense with the presence of the traditional, toxic fining agents (As2O3 and/or Sb2O3).
- Within the glass-ceramic materials of the invention, As2O3 and/or Sb2O3 are not present, supposing that they are present, in effective quantities, in reference to the fining of precursor glasses of the aforesaid glass-ceramic materials. If As and/or Sb are present, they are as trace elements, in quantities generally lower than 200 ppm. The presence of such traces can not be excluded. The aforesaid traces come, for example, from impurities in the raw materials used. The specific details above are given in reference to the circumlocution "containing, with the exception of inevitable traces, neither arsenic nor antimony" used in the present description and the appended claims, to qualify glass-ceramic materials and their precursor glasses.
- It may not, however, be excluded that the glass-ceramic materials of the invention contain others active compounds as a fining agent. It is only according to an advantageous embodiment that they do not contain such compounds.
- Within the scope of another embodiment, independent of the preceding, the glass-ceramic materials of the invention do not contain fluorine.
- Described below, are glass-ceramic materials of the first object of the invention whose composition, expressed in percentages of oxide weight, essentially consists of:
SiO2 50-75 advantageously 65-70 Al2O3 17-27 advantageously 18-22 Li2O 2-6 advantageously 2.5-4 MgO 0-5 advantageously 0.5-2 ZnO 0-5 advantageously 1-3 TiO2 0-5 advantageously 1.5-3.5 ZrO2 0-5 advantageously 0-2.5 BaO 0-3 advantageously 0-2 SrO 0-3 advantageously 0-2 CaO 0-3 advantageously 0-2 Na2O 0-3 advantageously 0-1 K2O 0-3 advantageously 0-1.5 P2O5 0-8 advantageously 0-3 B2O3 0-3 SnO2 0.15-0.3 advantageously 0.15-0.25 CeO2 and/or MnO2 0.7-1.5 advantageously 0.8-1.5 - The advantageous ranges indicated above are to be considered independently of one another and in combination with one another. Thus, the glass-ceramic materials of the invention advantageously present the weight composition indicated above in the rightmost column.
- It has been indicated that the compositions in question "essentially consist of" the given list of oxides. This means that within the aforesaid compositions the sum of the listed oxides represents at least 95%, generally at least 98% by weight. Indeed, other elements such as lanthanum oxide, yttrium oxide, and dyes (see further), in small quantities, may be found within the aforesaid compositions.
- Concerning the ranges indicated for the quantity of action of SnO2 on one hand and CeO2 and/or MnO2 on the other, they are, in general, advantageously 0.15 to 0.25 and 0.8 to 1.5, respectively.
- These three remarks are also applicable to the glass-ceramic material compositions below.
- In application
EP-A-0 437 228 , the applicant described glass-ceramic materials with interesting properties, in particular rapid ceramming. Such glass-ceramic materials are advantageously related to the present invention. Thus are glass-ceramic materials also part of the first object of the invention whose composition expressed in percentages of oxide weight essentially consists of:SiO2 65-70 Al2O3 18-19.8 Li2O 2.5-3.8 MgO 0.55-1.5 ZnO 1.2-2.8 TiO2 1.8-3.2 BaO 0-1.4 SrO 0-1.4 with BaO+ SrO 0.4-1.4 with MgO+ BaO+ SrO 1.1-2.3 ZrO2 1.0-2.5 Na2O 0-<1.0 K2O 0-<1.0 with Na2O+ K2O 0-<1.0 With (2.8 Li2O+1.2 ZnO) /5.2 MgO >1.8 SnO2 0.15-0.3 CeO2 and/or MnO2 0.7-1.5 - As referred to above, the glass-ceramic materials of the invention are likely to contain dyes. Their composition is thus likely to contain an effective quantity (in reference to the coloring effect sought) of at least one dye. Said dye or dyes are advantageously selected from among CoO, Cr2O3, Fe2O3, NiO, CuO, and V2O5 (thus taken separately or in combination). Those skilled in the art are not unaware of that V2O5 (a metallic oxide dye whose metal element, vanadium, is likely to exist with several valences) is usually added to the mixture of raw materials to obtain dark glass-ceramic materials. Thus, glass-ceramic materials of the invention contain advantageously 0.03 to 0.15% vanadium oxide.
- The second object of the present invention relates to glass-ceramic articles as described above, said glass-ceramic material containing jointly in its composition SnO2 and CeO2 and/or MnO2 in the quantities specified above. The aforesaid articles can in particular consist of cook-tops, cooking utensils, microwave oven plates, fireplace windows, fire doors, fire windows, and pyrolysis- and catalysis-oven windows. Such a list is not exhaustive.
- The third object of the present invention relates to lithium alumino-silicate glasses, which are precursors of glass-ceramic materials of the invention, such as described above. The lithium alumino-silicate glasses, which jointly contain SnO2 and CeO2 and/or MnO2, in the quantities specified above, and which are precursors of the glass-ceramic materials of the invention, are in fact novel and therefore constitute the third object of the invention. Said novel glasses advantageously present a composition that corresponds to those specified above for the glass-ceramic materials of the invention.
- The aforesaid novel glasses present a composition which contains, except for inevitable traces, neither arsenic nor antimony. Advantageously, the aforesaid novel glasses only contain as a fining agent the combination "SnO2 + CeO2 and/or MnO2" within the meaning of the invention.
- The fourth object of the present invention relates to a method of preparing a glass-ceramic material of the invention, such as described above. Classically, said method comprises the heat treatment of a lithium alumino-silicate glass, which is a precursor of such a glass-ceramic material, under conditions which ensure its ceramming, the aforesaid glass containing, with the exception of inevitable traces, neither arsenic nor antimony. Such a ceramming treatment is known per se.
- Characteristically, according to the invention, it is carried out on the aforesaid glass whose composition, expressed in percentages by weight of oxides with respect to total weight, comprises:
- 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO2; and
- 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2.
- The glass-ceramic materials produced advantageously present a composition which corresponds to one of the compositions specified above for the glass-ceramic materials of the invention.
- The fifth object of the present invention relates to a method of preparing an article made from a glass-ceramic material of the invention. The aforesaid method classically comprises three successive steps as follows:
- the melting of a lithium alumino-silicate glass or a mineral filler, which is a precursor of such a glass, said glass or said filler containing, with the exception if inevitable traces, neither arsenic nor antimony, and containing an effective and non-excessive amount of at least one fining agent; followed by the fining the molten glass obtained;
- the cooling of the molten fined glass obtained and, simultaneously, its shaping into the form desired for the article sought;
- the ceramming of said shaped glass.
- Characteristically, according to the invention, the aforesaid glass or the aforesaid filler in question presents a composition which contains jointly tin oxide and cerium oxide and/or manganese oxide in the quantities below, expressed in percentages by weight of oxides with respect to total weight:
- 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO2; and
- 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2.
- The glass-ceramic material component of the article produced advantageously presents a composition which corresponds to one of the compositions specified above for glass-ceramic materials of the invention.
- Within the scope of the methods above, SnO2 and CeO2 and/or MnO2 act efficiently, in the quantities indicated, for the fining of precursor glass.
- It was indicated in addition that specific "SnO2 and CeO2 and/or MnO2" combinations described have a beneficial action on color stability (obtained by the action of at least one metallic oxide dye whose metallic element is likely to exist with several valences) at ageing of the glass-ceramic materials. Thus, according to a preferred embodiment of the methods above, the composition of glass or filler (precursor) includes an effective quantity of at least one metallic oxide dye whose metallic element is likely to exist with several valences (advantageously V2O5) and SnO2 and CeO2 and/or MnO2 act efficiently in the quantities indicated for the simultaneous fining of precursor glass and the stabilization of the color of the glass-ceramic materials during ageing. SnO2 and CeO2 and/or MnO2 act advantageously in the preparation of glass-ceramic material articles colored with vanadium, in the preparation of dark glass-ceramic plates, in particular, intended for cooking.
- As has been specified above, the reduction in the transmission of glass-ceramic materials during the ageing process is related to the continuation of the reduction of vanadium. The inventor thus observed, within the scope of this invention, that the presence of manganese and/or cerium oxide limits the reduction of vanadium and consequently makes it possible to better control glass-ceramic coloring properties.
- The invention, such as described above, can in addition be perfectly understood as a use invention. Thus it also has as an object:
- the use of SnO2 in combination with CeO2 and/or MnO2 in the following quantities, expressed in oxide percentages by weight of the composition of the aforesaid glass:
- a. 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO2; and
- b. 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2:
for the fining of a glass, precursor of a glass-ceramic material containing a solid solution of β-quartz or of β-spodumene(solid solutions of β-quartz and β-spodumene) as main crystalline phase(s), (the aforesaid glass and thus the aforesaid glass-ceramic material) containing, except for inevitable traces, neither arsenic nor antimony;
- the use of SnO2 in combination with CeO2 and/or MnO2 in the following quantities expressed in oxide percentages by weight of the composition of the aforesaid glass:
- a. 0.15 to 0.3%, advantageously 0.15 to 0.25%, of SnO2 and
- b. 0.7 to 1.5%, advantageously 0.8 to 1.5%, of CeO2 and/or MnO2,
for the stabilization of the color during ageing of the glass-ceramic materials obtained from said glass. - The invention will now be illustrated by the following examples.
- More precisely, examples E, F, H and I illustrate the aforesaid invention while examples A, B, C, D and G are comparative examples.
- Table 1 below indicates:
- in its first part, weight compositions of the glasses in question; and
- in its second part, the number of bubbles per cm3 of the aforesaid glasses.
- Glasses were prepared in the usual way from oxides and/or easily decomposable compounds such as nitrates and carbonates. The raw materials are mixed to obtain a homogeneous mixture.
- Approximately 800 g of raw materials were placed in silica crucibles. The crucibles were then introduced into a preheated furnace at 1,400 °C. They then underwent the following melting cycle:
- 160 min from 1,400 to 1,600 °C,
- 100 min from 1,600 to 1,650 °C,
- 110 min at 1,650 °C.
- The glasses were then rolled to a thickness of 6 mm and then heated at 650 °C for 1 h. The number of bubbles was automatically counted by a camera coupled to an image analyzer.
- Six batches were tested. They differ primarily by nature of the compound or compounds acting as a fining agent:
- the batch corresponding to example A contains arsenic oxide (As2O3: 0.6%) (and 0.2% of V2O5, as a dye);
- the batch corresponding to example B contains only tin oxide (SnO2: 0.2%);
- the batch corresponding to example C contains only cerium oxide (CeO2: 1%);
- the batch corresponding to example D contains tin oxide (SnO2: 0.2%) and cerium oxide (CeO2: 0.5%);
- the batch corresponding to example E contains tin oxide (SnO2: 0.2%) and cerium oxide (CeO2: 1%);
- the batch corresponding to example F contains tin oxide (SnO2: 0.2%) and manganese oxide (MnO2: 1%).
- Batches E and F illustrate the invention.
- The melting cycle is short in order to generate sufficient bubbles for the purpose of differentiating the fining performances of the various products tested (As2O3, SnO2, CeO2, SnO2 + CeO2, SnO2 + MnO2). It can be estimated that the glass obtained from this test with fewer than 400 bubbles/cm3 can be produced on an industrial scale with sufficient quality.
Table 1 Examples A B C D E F Composition (% by weight) SiO2 68.50 69.03 68.20 68.53 68.03 68.03 Al2O3 19.3 19.3 19.3 19.3 19.3 19.3 Li2O 3.5 3.5 3.5 3.5 3.5 3.5 MgO 1.1 1.1 1.1 1.1 1.1 1.1 ZnO 1.6 1.6 1.6 1.6 1.6 1.6 TiO2 2.6 2.6 2.6 2.6 2.6 2.6 ZrO2 1.8 1.8 1.8 1.8 1.8 1.8 BaO 0.8 0.8 0.8 0.8 0.8 0.8 SnO2 0.2 0.2 0.2 0.2 MnO2 1 CeO2 1 0.5 1 As2O3 0.6 V2O5 0.2 0.07 0.1 0.07 0.07 0.07 Number of bubbles/cm3 110 720 1,270 790 365 350 - The tests clearly show that SnO2 and CeO2, alone, at the quantities indicated (0.2 and 1% by weight, respectively), are much less effective as a glass fining agent than As2O3 used in the quantity indicated. The combination SnO2 + CeO2 with 0.2% SnO2 and 0.5% CeO2 is not much more effective. Surprisingly, the combinations SnO2 + CeO2 and SnO2 + MnO2 used in batches E and F give satisfactory results.
- Below is demonstrated that fining according to the invention does not significantly modify the properties (thermal dilation, color and transmission) of prepared glass-ceramic materials and that, on the contrary, a positive effect on ageing is observed.
- Glasses were prepared (prior art and invention) and cerammed; the properties of the ceramics obtained were then measured (following ceramming and after ageing).
- The raw materials were brought to 1,500 °C then melting was performed at 1,650 °C for 6 h. The glass was rolled to a thickness of 6 mm and reheated at 650 °C for 1 h.
- The pieces of glass were cerammed in a static oven according to the following heating schedule:
- 20 min from ambient temperature to 600 °C,
- 45 min from 600 to 820 °C,
- 20 min from 820 to 930 °C,
- 15 min at 930 °C.
- Following ceramming, measurements were taken of the thermal expansion coefficient, integrated transmission Y, and transmission at 1,050 nm. The transmissions were measured on a sample 3 mm in thickness. Y was measured using D65 illumination.
- Ageing is performed for 100 h at 700 °C in a static oven. After the aforesaid ageing, the thermal expansion coefficient, integrated transmission Y, and transmission at 1,050 nm are again measured.
- The compositions of glasses and glass-ceramic materials as well as the properties of the aforesaid glass-ceramic materials are given in Table 2 below.
Table 2 Examples G H I Composition (% by weight) SiO2 69.54 69.23 68.63 Al2O3 19.4 18.5 18.8 Li2O 3.6 3.4 3.5 MgO 1.1 1 1.1 ZnO 1.7 1.5 1.5 TiO2 2.5 2.6 2.7 ZrO2 1.9 1.7 1.7 BaO 0.8 0.8 SnO2 0.2 0.2 0.2 MnO2 1 CeO2 1 V2O5 0.06 0.07 0.07 After ceramming Expansion (25-700°C) (x10-7 K-1) 0.3 1.1 Y 3.7 4.4 1.4 T at 1,050 nm (%) 74.9 76 73 After ceramming and curing Expansion (25-700°C) (x10-7 K-1) 0.3 1.2 Y 2.3 4.4 1.2 T at 1,050 nm (%) 74.7 76.7 73 - The sample in example G (prior art) contains only tin oxide (SnO2), while those in examples H and I (invention) contain SnO2 + CeO2 and SnO2 + MnO2, respectively, in adequate quantities as a fining agent.
- After ageing, the parameter "integrated transmission Y" decreased significantly in example G. In examples H and I, the observed reduction is less. For the aforesaid examples H and I, ageing deteriorates neither integrated transmission Y nor transmission at 1,050 nm.
- Appended
figure 1 , which shows the transmission curves (T = f(λ)) of the products according to examples G (prior art) and H (invention), can also be considered. Actually, transmission as a function of wavelength was measured on samples 0.5 mm in thickness after ceramming (G', H') and after ceramming and ageing (G", H"). - For the sample in example G, which does not contain CeO2, the G' and G" curves present a valley between 400 and 500 nm. Absorption increases in this region with ageing. This absorption is attributed to the presence of vanadium in its most reduced form (V3+) (see "Optical Spectra of the various valence states of Vanadium in Na2O. SiO2 glass" by W.D. Johnston, Journal of the America Ceramic Society (48)12, p 608-610).
- For the sample in example H, which contains SnO2 + CeO2, such a valley neither exists for the H' curve (before ageing: after ceramming) nor for the H" curve (after ceramming and ageing). From this it can be deduced that the presence of cerium limits the reduction of vanadium by tin and thus leads to the formation of a smaller quantity of V3+, whether during ceramming or ageing.
Claims (12)
- A glass-ceramic material containing a solid solution of β-quartz or(and) of β-spodumene as main crystalline phase(s) and essentially free of arsenic and antimony, the composition of which, expressed in percentages by weight of oxides, essentially consists of: SiO2 50-75; Al2O3 17-27; Li2O 2-6; MgO 0-5; ZnO 0-5; TiO2 0-5; ZrO2 0-5; BaO 0-3; SrO 0-3; CaO 0-3; Na2O 0-3; K2O 0-3; P2O5 0-8; B2O3 0-3; SnO2 0.15-0.3, advantageously 0.15-0.25; CeO2 and/or MnO2 0.7-1.5, advantageously 0.8-1.5.
- The glass-ceramic material according to claim 1 , the composition of which, expressed in percentages by weight of oxides, essentially consists of: SiO2 65-70; Al2O3 18-22; Li2O 2.5-4; MgO 0,5-2; ZnO 1-3; TiO21.5-3.5; ZrO2 0-2.5; BaO 0-2; SrO 0-2; CaO 0-2; Na2O 0-1; K2O 0-1.5; P2O5 0-3; SnO2 0.15-0.25; CeO2 and/or MnO2 0.8-1.5.
- The glass-ceramic material according to 1 or 2, the composition of which, expressed in percentages by weight of oxides, essentially consists of: SiO2 65-70; Al2O3 18-19.8; Li2O 2.5-3.8; MgO 0.55-1.5; ZnO 1.2-2.8; TiO2 1.8-3.2; BaO 0-1.4; SrO 0-1.4, with BaO+SrO 0.4-1.4, with MgO+BaO+SrO 1.1-2.3; ZrO2 1.0-2.5; Na2O 0-<1.0; K2O 0-<1.0, with Na2O + K2O 0-<1.0, with (2.8Li2O+1.2ZnO)/5.2MgO >1.8; SnO2 0.15-0.3, advantageously 0.15-0.25; CeO2 and/or MnO2 0.7-1.5, advantageously 0.8-1.5.
- The glass-ceramic material according to any one of claims 1 to 3, the composition of which further comprises an effective amount of at least one colorant, advantageously selected from CoO, Cr2O3, Fe2O3, NiO, CuO and V2O5.
- An article made from a glass-ceramic material according to any one of claims 1 to 4, which notably consists of a cook-top, a cooking utensil, a microwave oven plate, a fireplace window, a fire-door, a fire-window, a pyrolysis-or catalysis-oven window.
- A lithium alumino-silicate glass, which is a precursor of a glass-ceramic material according to any one of claims 1 to 4, the composition of which corresponds to that of a glass-ceramic material according to any one of claims 1 to 4.
- A method of preparing a glass-ceramic material according to any one of claims 1 to 4, which comprises heat-treating a lithium alumino-silicate glass, which is a precursor of such a glass-ceramic material, under conditions which ensure its ceramming, said glass containing, with the exception of inevitable traces, neither arsenic, nor antimony, characterized in that the composition of said glass corresponds to that of a glass-ceramic material according to any one of claims 1 to 5.
- A method of preparing an article according to claim 5, which is made of a glass-ceramic material according to any one of claims 1 to 4, which method successively comprises:- melting a lithium alumino-silicate glass or an inorganic filler, which is a precursor of such a glass, said glass or said filler containing, with the exception of inevitable traces, neither arsenic, nor antimony and containing an effective and non-excess amount of at least one fining agent; followed by fining the molten glass obtained;- cooling the molten fined glass obtained and, simultaneously, shaping it into the shape desired for the article sought after;- ceramming said shaped glass,characterized in that the composition of said glass or said filler corresponds to that of a glass-ceramic material according to claims 1 to 4.
- The method according to claim 7 or 8, characterized in that SnO2 and CeO2 and/or MnO2 are effectively used, in the indicated amounts, for fining said precursor glass.
- The method according to claim 7 or 8, characterized in that the composition of said glass or said filler comprises an effective amount of at least one metallic oxide-type colorant, the metal of which is able to exist under different valences, advantageously consisting in V2O5; and in that SnO2 and CeO2 and/or MnO2 are effectively used, in the indicated amounts, for fining said precursor glass and stabilizing the color of the glass-ceramic material during aging.
- Use of SnO2 in combination with CeO2 and/or MnO2, in the below amounts, expressed in percentages by weight of oxides of the composition of said glass:- 0.15 to 0.3%, advantageously 0.15 to 0.25% of SnO2; and- 0.7 to 1.5%, advantageously 0.8 to 1.5% of CeO2 and/or MnO2,for the fining of a glass which is the precursor of a glass-ceramic material containing (i) a solid solution of β-quartz or(and) of β-spodumene as main crystalline phase(s), and (ii) with the exception of inevitable traces, neither arsenic, nor antimony.
- Use of SnO2 in combination with CeO2 and/or MnO2, in the below amounts, expressed in percentages by weight of oxides of the composition of said glass:- 0.15 to 0.3%, advantageously 0.15 to 0.25% of SnO2; and- 0.7 to 1.5%, advantageously 0.8 to 1.5% of CeO2 and/or MnO2, for:(A) fining a glass which is the precursor of a glass-ceramic material containing (i) a solid solution of β-quartz or(and) of β-spodumene as main crystalline phase(s) ; (ii) with the exception of inevitable traces, neither arsenic, nor antimony; and (iii) an effective amount of at least one metallic oxide-type colorant, the metal of which is able to exist under different valences, advantageously consisting in V2O5; and(B) stabilizing the color of the glass-ceramic material obtained from said glass during ageing.
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FR0512394A FR2902420A1 (en) | 2005-12-07 | 2005-12-07 | Glass-ceramic material useful for making article e.g. fireplace window, comprises stannic oxide in combination with ceric oxide and/or manganese dioxide, in specific amounts |
FR0512588A FR2902421B1 (en) | 2005-12-07 | 2005-12-13 | QUARTZ AND / OR B SPODUMENE GLASS VITROCERAMICS, PRECURSOR GLASSES, ARTICLES THEREOF, VITROCERAMIC VITROCERAMIC PRODUCTS AND ARTICLES THEREOF |
PCT/EP2006/069374 WO2007065910A1 (en) | 2005-12-07 | 2006-12-06 | Glass, glass-ceramic, articles and fabrication process |
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JP6027719B2 (en) | 2016-11-16 |
US20070129231A1 (en) | 2007-06-07 |
KR20080080615A (en) | 2008-09-04 |
ES2684754T3 (en) | 2018-10-04 |
US7473660B2 (en) | 2009-01-06 |
JP6134990B2 (en) | 2017-05-31 |
JP2015131760A (en) | 2015-07-23 |
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KR101385800B1 (en) | 2014-04-16 |
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